Polyvinyl acetal resin compositions containing the butyl ether of diethylene glycol succinate



- and more particularly.

' hereinafter appear.

Patented June 1c, 1941 ronyvmh CONTAININ THE Henry 1;. small, Rochester, Eastman Kodak Company,

CETAL SIN COMPOSITIONS BUTYL n'rnnn OF DI- ETBYLENEGLYCOL SUCCINATE N. Y.. assignor to Rochester, N. Y., a

corporation oi New Jersey No Drawing. Application January 24, 1939,

- Serial No. 252,619

This invention relates to plastic compositions,

to compodtions comprising a polyvinyl acetal resin a Y oi this invention is to produce matter which may be made into gent.

One object compositions oi permanently transparent, strong and flexible.

sheets or films oi desired thinness which are substantiallv waterprooi, are unailected by ordinary photographic fiuids and possess the desired properties oi a supp rt ior sensitive photographic coatings. Another object oi my invention is to produce compositions oi matter which can be made into sheets suitable ior use in shatter-prooi glass. Still another object is to produce compositions which can be rolled, extruded, molded or otherwise worked into relatively thick sheets and massive plastics. A

further object is to produce compositions suitartiflcial silk filaments, Other objects will able ior use in lacquers, wrappingv tissues and the like.

I have discovered that the butyl ether oi diethylene glycol succinate is a useful conditioning agent for polyvinyl acetal resins. Not only does it serve as a plasticizer in the accepted sense oi the term, increasing the flexibility and toughness oi polyvinyl acetal resin films, sheets, or other objects or masses containing it, but when used in amounts oi about 40 or more parts per 100 parts oi certain oi the polyvinyl acetal resins, namely the polyvinyl .a'cetal resins in which a predominating proportion oi the acetal groups are butyraldehydeacetal groups, it has an unusual and. remarkable eilect which I may call elasticizingl' That is to say. a heet oi a polyvinyl butyraldehyde acetal resin oontalnins about 40 or more parts oi the butyl ether oi diethylene giycolsuccinate per 100 parts oi resin possesses the property which, in the rubber industry, is known as nerve;" the prop oi stretching to a considerable extent when tension is exerted upon it, and returning to its original dimensions when the tension is released. This property renders such rubbery sheets, iacture oi shatter-prooi For the manuiacture oi cast films or sheets, the polyvinyl acetal resin and butyl ether oi diethylene glycol succinate may be dissolved in a suitable solvent or solvent mixture, such, ior instance, mixtures, ethylene chloride-methanol mixtures, etc., about 300 to 500 or more parts oi the solvent or solvent mixture being used per 100 parts oi the glass.

laminated,

sheets, which I shall call particularly useful in the manuand a conditioning as acetone, methanol, acetone-methanol able.

the presence oi resin. From about 5 to parts or more oi the butyl ether oi diethylene glycol succinate r 100 parts oi resin may be employed, dependin upon the nature oi the resin and thepurpose ior which the sheets are to be used. Suitable proportions oi the butyl ether oi dlethylene glycol succinate ior any resin and any purpose may be readily determined by experiment. For the manuiacture'oi sheets suitable ior photographic film base,

irom 5 to 25 parts of the butyl ether of diethylene glycol succinate per 100 parts of resin are suit- The resin solution is cast as a sheet, the solvent evaporated, and the sheet stripped irom the casting suriace.

Sheets ior use in laminated glass may be formed by casting, or may be made withoutthe use oi volatile solvent by extrusiomior example in the manner set forth in application Serial No. 147,934 of Johns. Kimble and Ernest C. 'Blackard, filed June 12,1937. For instance, 40 or more parts oi the butyl ether of diethylene glycol succinate and 100 parts oi a polyvinyl butyraldehyde acetal resin may be mixed in a suitable, jacketed. mixer, at a low temperature, for example 10 C., and the mixture may then be worked on hot rolls, in the manner described in U. S. Patent 2,048,686 oi F. R. Conklin, until complete homogenization has taken place. The mass thus produced may then be extruded through an annular die, and the tube so formed slit to form a sheet.

, The polyvinyl acetal resins can be prepared byv reacting polyvinyl alcohol with an aldehyde in an acetal condensation catalyst, e. g., a mineral acid. These resins can also be prepared by simultaneously de-esteriiying a polyvinyl aliphatic ester and reacting the de-esterification product with an aldehyde in the presence oi a de-esteriiying catalyst and acetal condensation catalyst. Mineral acids are catalysts ior acetal iormation." Among the polyvinyl acetal resins with which both deesterification and the butyl ether oi diethylene glycol succinate is useiul may be mentioned, as illustrative examples,

the polyvinyl iormaldehyde acetal. resins. the

polyvinyl acetaldehyde aoetal resins, the polyvinyl iormaldehyde acetaldehyde mixed acetal resins, the polyvinyl butyralde 'de acetal resins, and the polyvinyl butyraldeh e acetaldehyde mixed acetal resins.

Examples oi the preparation oi polyvinyl iormaldehyde acetal, resins may be mum in U. S. Patent 1,955,068, Examples 1, 4 and 5; in U. S. Patent 2,036,092, Examples 1, 2, 3, 7 and 8; in

British patent 454,691, Examples 1, 2, 3, 4, 5, 6

. in British 1 cipitated resin was and 7; in British Patent 404,279, Example 3; and 7 Patent 436,072, Examples 1, 2, 3, 4, 5, 6 and 7.

Examples of the preparation of polyvinyl acetaidehyde acetal resins may be found in U. 5. Patent 2,044,730, Example -1; U. S. Patent 1,955,- 068, Example 2; 4, 5 and 6; Brit Patent 466,598, Examples 1, 2, 3, 4 and 7; British Patent 404,279, Examples 1, 2, 4, 5, 6, 7 and 8; U. 8. Patent 1,990,399; and French Patent 808,578, Examples 1, 2 and 3. An additional example of the preparation of a polyvinyl acetaldehyde acetal resin is as follows:

50 pounds of polyvinyl acetate, the viscosity of whose molar solution in benzene was 45 centipoises, was dissolved in a mixture composed of 50 pounds of 95% ethyl alcohol and 90 pounds of ethyl acetate. To this solution was added 19.2 pounds of paraldehyde. Then acatalyst consisting of 5 pounds of 95% sulfuric acid diluted with 5 pounds of water was added. After thorough mixing, the reaction was allowed to proceed at 40. C. for 8 days. The reaction mixture was then diluted with acetone, and the resin precipitated by pouring into cold water, washed and dried. Analysis showed the resin to have an acetate group content equivalent to 3.3% of polyvinyl acetate and a hydroxyl group content equivalent to 6.5% of polyvinyl alcohol.

Examples of the preparation of polyvinyl formaldehyde acetaldehyde mixed acetal resins may be found in British patent 430,136, Examples 1, 2, 3, 4, 5 and 6; British Patent.445,565, Example 2; British Patent 465,873, Examples 1, 2, 3, 4, 5 and 6; French Patent 808,586, 'Examples 1, 2, 3, 4, 5, 6, 12, 13, 14, 15, 16, 17, 18 and 19. Additional examples oi the preparation of polyvinyl formaldehyde acetaldehyde mixed acetal resins are as follows: 100 parts (1.16 mole calculated as mOnOmeric vinyl acetate) of a polyvinyl acetate (45 centipoises), 100 parts of ethyl alcohol, 180 parts of ethyl acetate, 34 parts (.77 mole as monomeric acetaldehyde) .of paracetaldehyde .and 5.8 parts (.196 mole as monomeric formaldehyde) of paraformaldehyde were placed in an enamelled vessel and brought into solution by stirring. When solution was complete, 10 parts of sulfuric acid (sp. gr. 1.84) in 10 parts of water was added, and the mixture stirred. The mixture was maintained at a temperature of C. for 144 hours. The-contents of the vessel were then diluted with about two and a half volumes of acetone, and the mixture precipitated by pouring into water. The prewashed free from impurities by repeated changes of cold water, and dried. The resin, when analyzed, gave a hydroxyl group content equivalent to about 6.4 per cent by weight of polyvinyl alcohol, an acetate group content equivalent to about 4.0 per cent by weight of polyvinyl acetate, a formaldehyde acetal group content equivalent to about 15.9 per cent by weight of polyvinyl formaldehyde acetal and an acetaldehyde acetal group content equivalent to about 73.9 per cent by weight of polyvinyl acetaldehyde acetal. .The polyvinyl acetal portion of the resin was therefore made up of about 19.7 per cent by'moles of polyvinyl formaldehyde acetal and about 80.3 per cent by moles of polyvinyl aoetaldehyde ac'etal. The resin was soluble in acetoneto an extent which permitted coating 9. film or sheet from the resin.

50 parts (.58 mole-as monomer) of polyvinyl acetate centipoises), parts of ethyl alcohol, 90 parts of ethyl acetate, 17 parts (.385111016 as U. S. Patent 2,036,092, Examples monomer) of paracetaldehyde, 2.9 parts" (.09- mole as monomer) of paraformaldehyde, 5 part of sulfuric acid and 5 parts of water were treatei as in Example 1 for 161 hours. The well washer and dried resin gave upon analysis a hydroxy group content equivalent to about 9.6% by weigh1 of polyvinyl alcohol, an acetate group conteni equivalent to about 4.1% by weight of polyvinyi acetate, a formaldehyde acetal group content was continued for a further vinyl acetal portion of the equivalent to about 13.9 per cent by weight of polyvinyl formaldehyde acetal, and an acetaldehyde acetal group content equivalent to about 69.9 per cent of polyvinyl acetaldehyde acetal. The polyvinyl acetal portion of the resin was therefore made up of about 18.5 per cent by moles of polyvinyl formaldehyde acetal and 81.5 per cent by moles of polyvinyl acetaldehyde acetal. The resin was soluble in acetone to an extent which permitted coating 9. film or sheet from the resin.

1300 parts (15.1 mole as monomer) of a polyvinyl acetate (45 centipoises), 1700 parts of ethyl acetate, 2250 .parts of ethyl alcohol (95%) and 48 parts (1.57 mole as monomer) of parafoimaldehyde (trioxy'methylene) were placed in a vessel equipped with a refluxcondenser and a means of agitation, and the contents brought to a temperature of about C. by means of steam heating. 182.25 parts of sulfuric acid (sp. gr. 1.84) dissolved in 51.5 parts of water were added. and the whole was heated at about 70 C. for about five hours, agitating throughout. At this point 266.4 parts (6.05 mole as monomer) of paracetaldehyde were added, and heating at about 70 C. with agitation period of twenty hours. The contents of the reaction vessel were neutralized with ammonium hydroxide and diluted with water precipitating the resin as a cake.

The cake was cut into small pieces and repeatedly washed with hot water until of polyvinyl acetate, the remainder of the weight of the resin being polyvinyl acetal. The polyresin was made up of about 80 per cent by moles of polyvinyl acetaldehyde acetal and about 20 per cent by moles of polyvinyl formaldehyde ,acetal. The resin was not quite soluble in acetone, but could be made to dissolve by admixing small amounts of other solvents, such as alcohols, with the acetone.

Examples of the preparation of polyvinyl butyraldehyde acetal resins may be found in U. 8. Patent 2,044,730, Examples 2, 5 and 6; British Patent 466,598, Example 5; French Patent 813,303, Example 1; FrenchPatent 813,514, Examples 1, 2, 3 and 4; and British Patent 459,878, Examples 1, 2, 5, 6, 7, 8, 9 and 10. An additional example of the preparation of a polyvinyl butryaldehyde acetal resin is as follows:

20 pounds of polyvinyl acetate, the viscosity of whosemolar solution in benzene was 45 centi- 1301888, was

the diluted mixture into content of 1.8%and a residual polyvinyl alcohol content equivalent to" 4.8% by weight of polyvinyl alcohol.

An example of the preparation of a polyvinyl butyraldehyde acetaldehyde mixed acetal. resinis given in French Patent 813,303, Example '2.

A further example resin is as-follows:

of the preparation of a polyvinyl butyraldehyde acetaldehyde mixed acetal tal, of which 51% 143 pounds of polyvinyl acetate or 25 centi-' poises. viscosity was dissolved in- 357 pounds of dehyde, and 35.7 pounds of 35% hydrochloric acid. The contents of the container were well mixed and allowed to stand for four days at40 C., then diluted with approximately 3 volumes of ethyl alcohol.

- ethyl a1cohol.. To this solution are added 35.9 pounds of butyraldehyde, 51.2 pounds of paraldeether of diethylene glycol succinate as an elasti- It was a mixed polyvinyl acewas polyvinyl acetaldehydc was polyvinyl butyraldehyde content of 8.0%.

acetal and 32.1% acetal. Y v

What I claim as my invention and desire to be secured by Letters Patent-of the United States is:

1. A transparent, rubbery sheet comprising 100 parts of a polyvinylacetal resin in which a predominating proportion of the acetal groups are butyraldehyde acetal groups, and at least 40 parts,

approximately, of the butyl ether of diethylene glycol succinate as an elasticizer therefor.

.2. A transparent, rubbery sheet comprising 100 parts of a polyvinyl butryaldehyde acetal resin and at least 40 parts, approximately, of the butyl cizer therefor.

- HENRY B. SMITH. 

